JP3251726B2 - Coating composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition, and more particularly to a coating composition excellent in oil resistance, impact resistance, abrasion resistance and the like.

[0002]

2. Description of the Related Art In recent years,
Attempts to use various plastics have been studied for the purpose of reducing the weight of glass plates for windows of transport aircraft such as aircraft, automobiles, buses, trucks, railway vehicles, and ships. The window glass of such a transport machine has abrasion resistance (surface pencil hardness of 6) which is not damaged by repeated use of a dirty cleaning brush.
H), oil and chemical resistance (no crazing, cracking, or whitening) to gasoline splatters and aircraft cleaners, lighter weight to reduce fuel consumption, impact resistance to vibration and impact during travel and flight In addition, conditions such as transparency (visible light transmittance of 90% or more) sufficient for ensuring visibility and safety are required.

As an alternative to glass products, studies have been made to form a transparent resin film on the surface of a polycarbonate or acrylic molded product to improve abrasion resistance, oil resistance and the like. For example, JP-A-2-178359 discloses a molded article coated with a resin using urethane acrylate containing mono- and di (meth) acryloxyethyl esters of phosphoric acid. However, such a resin coating has a surface pencil hardness of about 5H and is scratched and fogged by a cleaning brush or the like to which rust or sand adheres, so that it can be used as a substitute for a window glass of a transport machine. Did not.

Japanese Patent Application Laid-Open No. Hei 4-309568 discloses a coating agent containing tri (meth) acryloxyethyl ethyl phosphate, but has a surface pencil hardness of about 2H. It does not have abrasion resistance that can be used as a substitute for glass.

[0005] An object of the present invention is to solve such conventional problems and to impart excellent oil resistance, impact resistance and abrasion resistance to the surface of a polycarbonate or acrylic molded product, and to replace a window glass for a transport machine. An object of the present invention is to provide a coating composition which can be used as an article.

[0006]

Means for Solving the Problems The coating composition of the present invention is characterized by containing a phosphinylphosphimide compound represented by the following formula (I) as an active ingredient.

[0007]

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(Where R represents H or CH ₃ ) The phosphinylphosphimide ester represented by the above formula (I) used in the present invention can be produced by a general production method. For example, it can be produced by reacting hydroxyethyl (meth) acrylate and pentachlorophosphinylphosphimide in an inert non-aqueous solvent in the presence of a deoxidizing agent. Inactive non-aqueous solvents used in this reaction include benzene, toluene, xylene, chloroform, methylene chloride, cyclohexane, ether,
There are tetrahydrofuran, 1,4-dioxane and the like, and as a deoxidizing agent, tertiary amines such as triethylamine, N, N, N-tetraethylenediamine, pyridine and the like can be mentioned.

The production of pentachlorophosphinylphosphimide can be carried out by reacting phosphorus pentachloride and ammonium sulfate in chlorobenzene as shown in the formula (II).

[0010]

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[0011] In the coating composition of the present invention,
In addition to the phosphinylphosphimide compound described above, a monofunctional monomer and / or a polyfunctional monomer copolymerizable with the compound may be contained. In this case, the use ratio of the phosphinylphosphimide compound and the monomer is not particularly limited and can be appropriately selected from a wide range. It is preferable that the number of polymerizable functional groups in the entire composition of the polymer and the monomer be 2.5 or more per molecule. Since the phosphinylphosphimide compound has five polymerizable functional groups per molecule, for example, when mixed in equimolar amount with a monofunctional monomer having one polymerizable functional group, Six polymerizable functional groups are contained for a total of 2 mol of the ruphosphimide compound and the monofunctional monomer, and the number of polymerizable functional groups per molecule is three.
As described above, the number of polymerizable functional groups per molecule can be specified, and as described above, the phosphinylphosphimide compound and the monomer are mixed so that the number of polymerizable functional groups per molecule becomes 2.5 or more. Can be mixed with the body. Further, a more preferable amount of the polymerizable functional group per molecule is 3
10 to 10. If the amount of the polymerizable functional group per molecule is less than 2.5, the effects of the present invention may not be obtained in oil resistance, impact resistance, abrasion resistance and the like.

Examples of the monofunctional monomer and polyfunctional monomer copolymerizable with the phosphinylphosphimide include, for example, methyl acrylate, hydroxyethyl acrylate, ethylene glycol diacrylate, and triethylene glycol diacrylate. And methacrylates, glycidyl acrylate, 2,2′-bis (acryloxyphenyl) propane, 2,2′-bis [4-
(3-methacryloxy) -2-hydroxypropoxyphenyl] propane, vinyl acetate, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and 2-acryl (or methacryl) oxyethoxy phosphazene, mono- or dihydroxyethyl phosphate Acrylic or methacrylic ester of tris-2-
Acrylic (or methacrylic) oxyethoxy phosphate and the like can be mentioned.

In the coating composition of the present invention, various commonly used additives can be added as required. Examples of such additives include curing initiators such as azobisisobutyronitrile and benzoyl peroxide used in ordinary coating agents, photosensitizers such as 1-hydroxycyclohexyl phenyl ketone and p-methoxybenzophenone, Various additives such as a polymerization inhibitor, a colorant, an antioxidant, and an ultraviolet absorber can be exemplified.

Further, in the coating composition of the present invention,
If necessary, a filler or a lubricant can be contained. Examples of the filler include mica, silica, talc, alumina, apatite, glass beads, powders such as barium silicate, silicon nitride, silicon carbide, and potassium titanate, whiskers, and organic fillers such as polymethyl methacrylate. As the lubricant, solid, liquid, grease-like properties can be used,
For example, silicone-based, fluorine-based, other synthetic lubricants,
Teflon fine particles, molybdenum disulfide and the like can be used.

In the present invention, the phosphinylphosphimide compound represented by the above formula (I), which is an active ingredient, is usually in a liquid state, and can be used as it is in the composition of the present invention.

The composition of the present invention may be prepared by adding a monomer copolymerizable with the phosphinylphosphimide compound and the above-mentioned additives to the phosphinylphosphimide compound. In the present invention, the coating composition of the present invention may be diluted with an appropriate solvent and used in consideration of the material of the substrate to be applied, workability, and the like. The solvent is not particularly limited as long as it can dissolve or disperse the components of the composition of the present invention, and examples thereof include water, an aqueous solvent, and an organic solvent. As specific examples of the aqueous solvent, for example, a mixture of water and alcohols, as specific examples of the organic solvent,
For example, acetone, ketones such as methyl ethyl ketone,
Examples include aromatics such as benzene and toluene, halogens such as chloroform and methylene chloride, alcohols such as ethanol and propanol, ethers such as tetrahydrofuran and dioxane, and alicyclics such as cyclohexane and cyclohexanone. In addition, the dilution ratio is not particularly limited, and may be appropriately determined in consideration of, for example, workability.

In applying the coating composition of the present invention to a substrate, the composition or a solution or dispersion thereof may be applied to the substrate and cured. The coating method is not particularly limited, and a known method can be adopted. For example, a dipping method,
Spray method and the like can be mentioned.

Curing can be performed at room temperature, but heat curing, light curing, and electron beam curing are preferable in consideration of the characteristics of the resulting film. In this case, it is preferable to contain a reaction initiator or a sensitizer, for example, a reaction initiator such as benzoyl peroxide, di-t-butyl peroxide, p-methoxybenzophenone, 1-hydroxycyclohexyl phenyl ketone, dibenzoyl and the like. A sensitizer can be used, and its content is preferably about 0.05 to 5% by weight.

Further, a cured film of the coating composition of the present invention is formed on a substrate, punched out together with the substrate in accordance with the product shape, mounted on a mold, and molded simultaneously with injection molding. A CFI process for forming a protective film made of the coating composition of the present invention on the surface may be employed.

Further, the substrate to which the coating composition of the present invention can be applied is not limited to polycarbonate and acrylic, but may include other resin molded articles, metal molded articles, inorganic molded articles, and the like. it can.

[0021]

The coating composition of the present invention contains a phosphinylphosphimide compound represented by the above formula (I) and is polymerized to provide excellent oil resistance, impact resistance and abrasion resistance. And so on. Further, since the coating composition of the present invention contains the above-mentioned phosphinylphosphimide compound, it is flame-retardant due to the properties of phosphorus atoms.
Exhibits heat resistance of 50 ° C or higher.

Further, the coating composition of the present invention hardly peels off even when exposed to acid or alkali for a long time, and can be a stable film for a long time. The coating composition of the present invention has such excellent oil resistance,
It has impact resistance, abrasion resistance, and the like, and can be suitably used, for example, as a window material of a transport device such as an automobile, a sunroof material, or a cover material of lights. In addition, the coating composition of the present invention is not limited to the use of the window material of such a transport machine, for example, a coating composition for surface coating of tiles, outer walls of buildings or houses, steel towers and piers, and manholes. It can also be used as a product. Furthermore, it can also be used as a coating such as a clear coat for automotive exterior panels.

[0023]

EXAMPLES Penta (acryloxyethyl) phosphinylphosphoyl
In a glass reactor equipped with a stirrer, 1.5 mol of phosphorus pentachloride, 0.4 mol of ammonium sulfate and 1 liter of chlorobenzene were charged and reacted under reflux for 5 hours. After the reaction, excess ammonium sulfate was filtered off, chlorobenzene was distilled off, and crystallization was performed to obtain 0.8 mol of pentachlorophosphinylphosphimide.

In a light-shielded glass reactor, 0.2 mol of pentachlorophosphinylphosphimide obtained above is dissolved in chloroform, and 1.1 mol of triethylamine is added. A chloroform solution of -hydroxyethyl acrylate was added dropwise under ice-cooling, and the mixture was reacted under stirring at 25 ° C or lower for 2 days. After the reaction, wash with water,
After dehydration and drying with sodium sulfate, chloroform was distilled off under reduced pressure to obtain the desired penta (acryloxyethyl) phosphinylphosphimide in a yield of 95%.

As shown in FIG. 1, the IR spectrum of this substance is C = O at 1730 cm ⁻¹ , C = C at 1620 m ⁻¹ ,
The characteristic absorption of P = N is shown at 1200 cm ⁻¹ ,
^{In 1} H-NMR (CDCL ₃ ), PO was found at 4.35 ppm.
CH ₂ CH ₂ O, 5.80 to 6.50 ppm H ₂ C =
An absorption based on CH was observed, and ³¹ P-NMR (CDCL
_{In 3} ), O = P ester at -1 ppm, -13 ppm
Since the absorption based on the N = P ester is observed,
It was confirmed that the compound had the structure of the formula (I).

Example 1 (Preparation of coating liquid 1 ) 0.2 g of 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone was added to 20 g of penta (acryloxyethyl) phosphinylphosphimide. Was added and stirred and dissolved at room temperature to prepare a photocurable coating solution.

Example 2 (Preparation of coating liquid 2 ) 10 g of tri (methacryloxyethyl) phosphate and 10 g of penta (acryloxyethyl) phosphinylphosphimide were mixed, and 1-hydroxycyclohexylphenylketone was used as a sensitizer. 0.3 g was added to prepare a photocurable coating solution.

Example 3 A coating solution 1 was applied to a 3 mm-thick transparent polycarbonate plate (trade name: Panlite, manufactured by Teijin Chemicals Ltd.) so that the coating thickness became 10 μm, and 10 mm from a distance of 20 cm.
The protective film was formed by irradiating a 0 W high-pressure mercury lamp so that the integrated light amount became 2500 mJ / cm ² .

Table 1 shows the physical properties of the obtained polycarbonate plate with a protective film. The oil resistance was determined by visual observation of the appearance of a test piece immersed in gasoline for 1 hour at room temperature. The impact resistance was 15 mm in diameter from a height of 2 m for 20 test pieces.
Were evaluated by observing the state after falling of the steel ball. Further, the transparency is measured according to JIS K 7105.

Example 4 A coating solution 2 was applied on a transparent polycarbonate plate having a thickness of 3 mm (trade name: Panlite, manufactured by Teijin Chemicals Ltd.) so that the coating thickness became 10 μm, and a coating solution 2 was applied from a distance of 20 cm.
The protective film was formed by irradiating a 0 W high-pressure mercury lamp so that the integrated light amount became 3000 mJ / cm ² .

Table 1 shows the physical properties of the obtained polycarbonate plate with a protective film. Example 5 A coating solution 1 was applied to a 3 mm-thick transparent acrylic plate (manufactured by Kyowa Gas Chemical Industry Co., Ltd., trade name: Como Glass) so that the film thickness was 10 μm, and 10 mm from a distance of 20 cm.
The protective film was formed by irradiating a 0 W high-pressure mercury lamp so that the integrated light amount became 2500 mJ / cm ² .

Table 1 shows the physical properties of the obtained polycarbonate plate with a protective film. Comparative Example 1 Using a coating liquid 3 (commercially available silicone-based coating agent), coating was performed in the same manner as in Example 1, and heated at 90 ° C. for 1 hour to form a protective film.

Table 1 shows the physical properties of the obtained polycarbonate plate with a protective film. Comparative Example 2 Using Coating Solution 4 (commercially available acrylic coating agent)
It was applied in the same manner as in Example 2 to form a protective film.

Table 1 shows the physical properties of the obtained polycarbonate plate with a protective film. Comparative Example 3 A transparent glass plate having a thickness of 3 mm was evaluated in the same manner as in the example without any treatment, and the physical properties are shown in Table 1.

Comparative Example 4 A 3 mm thick transparent polycarbonate plate (manufactured by Teijin Chemicals Ltd., trade name: Panlite) was evaluated without treatment in the same manner as in the example, and each physical property is shown in Table 1.

[0036]

[Table 1]

As is evident from Table 1, the polycarbonate plates of Examples 3 to 5 in which the coating composition according to the present invention was used as a protective film were excellent in oil resistance, impact resistance and transparency, and were not less than 6H. Shows pencil hardness.

[Brief description of the drawings]

FIG. 1 is a diagram showing an IR spectrum of penta (acryloxyethyl) phosphinylphosphimide, which is an example of a phosphinylphosphimide compound according to the present invention.

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Takashi Kameshima 463 Kagasuno, Kawauchi-cho, Tokushima-shi, Otsuka Chemical Co., Ltd. Tokushima Research Laboratory (56) References JP-A-61-111379 (JP, A) JP-A-49 -18125 (JP, A) JP-B-47-45727 (JP, B1) JP-B-47-45726 (JP, B1) Polymer, vol. 36, No. 4, p. 713-718 (1995) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 4/02 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A coating composition comprising a phosphinylphosphimide compound represented by the following formula (I) as an active ingredient. Embedded image (Where R represents H or CH ₃ )